The Optoelectronic Nose: Colorimetric and Fluorometric Sensor Arrays

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Cite This: Chem. Rev. XXXX, XXX, XXX−XXX

The Optoelectronic Nose: Colorimetric and Fluorometric Sensor Arrays Zheng Li,† Jon R. Askim,‡ and Kenneth S. Suslick*,† †

Department of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States

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‡

ABSTRACT: A comprehensive review on the development and state of the art of colorimetric and fluorometric sensor arrays is presented. Chemical sensing aims to detect subtle changes in the chemical environment by transforming relevant chemical or physical properties of molecular or ionic species (i.e., analytes) into an analytically useful output. Optical arrays based on chemoresponsive colorants (dyes and nanoporous pigments) probe the chemical reactivity of analytes, rather than their physical properties (e.g., mass). The chemical specificity of the olfactory system does not come from specific receptors for specific analytes (e.g., the traditional lock-and-key model of substrate−enzyme interactions), but rather olfaction makes use of pattern recognition of the combined response of several hundred olfactory receptors. In a similar fashion, arrays of chemoresponsive colorants provide high-dimensional data from the color or fluorescence changes of the dyes in these arrays as they are exposed to analytes. This provides chemical sensing with high sensitivity (often down to parts per billion levels), impressive discrimination among very similar analytes, and exquisite fingerprinting of extremely similar mixtures over a wide range of analyte types, in both the gas and liquid phases. Design of both sensor arrays and instrumentation for their analysis are discussed. In addition, the various chemometric and statistical analyses of high-dimensional data (including hierarchical cluster analysis (HCA), principal component analysis (PCA), linear discriminant analysis (LDA), support vector machines (SVMs), and artificial neural networks (ANNs)) are presented and critiqued in reference to their use in chemical sensing. A variety of applications are also discussed, including personal dosimetry of toxic industrial chemical, detection of explosives or accelerants, quality control of foods and beverages, biosensing intracellularly, identification of bacteria and fungi, and detection of cancer and disease biomarkers.

CONTENTS 1. Introduction to Chemical Sensing and Optical Sensors 1.1. Nonoptical Sensors 1.2. Optical Sensors 2. Optical Array Sensing: Concepts and Sensors 2.1. Basis of Intermolecular Interactions 2.2. Classification of Colorimetric and Fluorometric Sensor Elements 2.2.1. Lewis Acid/Base Dyes 2.2.2. Brønsted Acid/Base Dyes 2.2.3. Redox Indicator Dyes 2.2.4. Solvatochromic or Vapochromic Dyes 2.2.5. Chromogenic Aggregative Indicators 2.2.6. Displacement Strategies for Fluorescent Sensors 2.2.7. Molecularly Imprinted Sensors 3. Sensor Fabrication and Instrumentation 3.1. Array Fabrication: Substrate Considerations 3.1.1. Printed Arrays 3.1.2. Fiber Optic Arrays 3.2. Instrumentation: Digital Imaging of Colorimetric and Fluorometric Sensors

© XXXX American Chemical Society

3.2.1. Digital Imaging of Colorimetric Sensor Arrays 3.2.2. Cell-Phone-Based Microplate Reader 4. Statistical Analysis and Modeling 4.1. Descriptive Methods 4.1.1. Hierarchical Cluster Analysis (HCA) 4.1.2. Principal Component Analysis (PCA) 4.2. Classification Methods 4.2.1. Linear Discriminant Analysis (LDA) 4.2.2. Support Vector Machines (SVMs) 4.2.3. Artificial Neural Networks (ANNs) 5. Applications of Colorimetric and Fluorometric Sensor Arrays 5.1. Applications to Single Analytes 5.1.1. Volatile Organic Compounds 5.1.2. Toxic Industrial Chemicals 5.1.3. Aqueous Analytes 5.1.4. Explosives 5.1.5. Accelerants and Postcombustion Residues

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Special Issue: Chemical Sensors

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Received: April 6, 2018

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DOI: 10.1021/acs.chemrev.8b00226 Chem. Rev. XXXX, XXX, XXX−XXX

Chemical Reviews 5.2. Applications to Complex Mixtures 5.2.1. Foods and Beverages 5.2.2. Proteins 5.2.3. Ratiometric Fluorometry for Intracellular Sensing 5.2.4. Bacteria and Fungi 5.2.5. Cancer and Disease Biomarkers 6. Conclusions and Future Challenges Author Information Corresponding Author ORCID Notes Biographies Acknowledgments References

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based on electrical responses as alternatives to electronic noses. Among these, optical sensors are especially noteworthy.44−49 The most common optical sensors are based on colorimetric or fluorescent changes originating from intermolecular interactions between the chromophore or fluorophore with the analytes.44 Combining array-based techniques that employ a chemically diverse set of cross-reactive sensor elements with novel digital imaging methods,50−58 one can produce a composite pattern of response as a unique optical “fingerprint” for any given analyte.27,59,60 By analogy, such optical sensor arrays are often referred to as optoelectronic noses or tongues.61 Optical arrays based on chemoresponsive colorants (dyes and nanoporous pigments) probe the chemical reactivity of analytes, rather than their physical properties. This provides a high dimensionality to chemical sensing that permits high sensitivity (often down to parts per billion (ppb) or even parts per trillion (ppt) levels), impressive discrimination among very similar analytes, and fingerprinting of extremely similar mixtures over a wide range of analyte categories, in both gaseous and liquid phases. Colorimetric and fluorometric sensor arrays therefore effectively overcome the limitations of traditional array-based sensors that solely depend on physisorption or nonspecific chemical interactions. Such optical array sensing has shown excellent performance in the detection and identification of diverse analytes, ranging from chemical hazards to energetic explosives, to medical biomarkers, and to food additives. To this end, a comprehensive review will be presented on the development and state of the art of optical array sensing technologies, mainly focused on colorimetric and fluorometric sensor arrays. We will cover recent advances and progress with such sensor arrays and their applications in the detection of volatile organic chemicals (VOCs), explosive screening, food and beverage inspection, as well as disease diagnosis; several commonly used methods for multivariate analyses of the highdimensional data will also be briefly introduced. Finally, some perspectives regarding the development of the next generation of optical sensors and other chemical sensing techniques will be presented. New sensor technologies must inevitably face the dilemma of attempting to create sensors that are both increasingly sensitive and increasingly robust; beyond a certain point, the more sensitive a sensor is, the less robust it inherently becomes due to poisoning during usage in real-world situations. Aging of sensors is a particularly acute problem for any sensor array that is intended to be reusable, regardless of the class of sensors. For pattern recognition to work (inherent in the concept of any kind of “nose” technology), the library of patterns must be representative of the sensors’ responses in immediate time of application; if sensor response drifts, then libraries can become obsolete very quickly. One path around this dilemma is to develop disposable sensors, thus unlinking the opposing demands that challenge the development of chemical sensing.61,62 Present array-based detectors have employed a variety of analytical strategies to trace even subtle changes in either physical properties (e.g., molecular weight, conductivity, surface tension) or chemical reactivity (e.g., Lewis acidity/basicity, hydrogen bonding, redox potential), including the use of conductive polymers and polymer composites, metal oxide semiconductors, quartz crystal microbalances, polymer coated surface acoustic wave devices, and fluorescent molecular frameworks. The chemical sensors that have been reported so far for odorant analysis, generally, can be categorized by their

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1. INTRODUCTION TO CHEMICAL SENSING AND OPTICAL SENSORS Chemical sensing aims to detect subtle changes in the chemical environment by transforming relevant chemical or physical properties of molecular or ionic species (i.e., analytes) into an analytically useful output.1−3 The prototypical example of chemical sensing is the olfactory system of animals. Even for humans beings, who are generally more visual than olfactory creatures, the sense of smell is one of our most basic capabilities, and we are able to recognize and discriminate over 10 000 individual scents, and possibly even billions.4,5 The chemical specificity of the olfactory system does not come from specific receptors for specific analytes (e.g., the traditional lock-and-key model of substrate−enzyme interactions), but rather olfaction makes use of pattern recognition of the combined response of several hundred olfactory receptors. For typical terrestrial mammals, there are ∼1000 semispecific olfactory receptor genes, which accounts for ∼3% of the entire genome;6−8 even humans have some 400 active olfactory receptors.9 Despite the complicated and speculative structures of the transmembrane olfactory receptors (the largest class of G-protein-coupled receptors4,7), a large fraction of them are believed to be metalloproteins that are highly reactive to numerous odorant molecules through coordination of the analyte to the metalbinding site.10−13 There is a pressing demand to develop effective methodologies that enable rapid, sensitive, portable, and inexpensive detection of toxic analytes in gases or aqueous solutions. Arraybased sensor technologies, or “electronic noses”,14−23 use several to many different cross-reactive sensors that interact with analytes, most commonly through physical adsorption, and generate an electrical response (e.g., changes in resistance or capacitance). The pattern of the sensor array, due to the crossreactivity of the individual sensors, enables molecular recognition by comparison to a predetermined library of responses. The first example of an artificial nose was reported by Persaud et al. in 1982, who tried to mimic the biological olfactory system using semiconductor transducers that were semispecific to analytes:24 three different metal oxides were employed to sense similar mixtures and discriminate among them. In recent years, an increasing number of cross-reactive analytical devices have emerged and have been applied to environmental monitoring,25−29 security screening,30−33 biomedical diagnosis,34−39 and food inspection.40−43 The vigorous development of novel techniques in chemical sensing has resulted in the availability of many useful sensors not B


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signal transduction approaches into optical and nonoptical types.63 The classification of these sensors is based primarily upon their use of either the physical properties of the analytes or the chemical interactions of the analytes. Electrochemical sensors detect signal changes in resistance, for example, induced by an electrical current passing through the electrodes which contact and interact with chemical analytes. Mass sensors measure differences in the mass of the sensor surface upon exposure to analytes. Optical sensors convert changes in electromagnetic waves (e.g., UV−vis light) into electronic signals. This review will begin with a brief introduction of these classes of sensors, followed by detailed discussions of the concepts, fabrication methods, and applications of optical array sensing technology.

from aging also poses a major challenge to the development of electrochemical sensors.93 Surface modification of electrochemical sensor surfaces can provide for improved selectivity, especially for bioanalytical applications, for example with molecular imprinted membranes94−97 or aptamers,98−101 but at the expense of added complexity and susceptibility to drift from irreversible chemical reactions. Surface modification of electrochemical sensors has also had success using various nanostructures; the enhanced sensitivity is largely due to the extremely high surface area to volume ratio inherent to nanoparticles.81,88 Nanowires, nanotubes, nanofibers, nanospheres, graphene, and other twodimensional layered materials have thus far shown great promise, although selectivity among similar analytes can be problematic.65,81 Hybrid structures of these nanomaterials are likewise excellent candidates for chemical sensors and have drawn significant attention in the past decade. Owing to the low dimensionality of the data resulting from most present incarnations of these sensors, engineering chemical selectivity into these systems remains the key to the future success for applications in chemical sensing or biosensing. Another class of nonoptical sensors is based on the detection of small changes in the sensor’s mass upon exposure to chemical analytes through physisorption of analytes onto the sensor or from specific chemical reactions of the analytes with the sensor. Mass sensors are generally microelectromechanical systems (MEMS).102 A typical mass sensor is a piezoelectric resonator with an absorbing polymer or molecular receptor coating. Molecular analytes are adsorbed on or absorbed in the film of the sensor, increasing the mass of the sensor and thus decreasing in the resonant frequency. A typical example of mass sensors is the quartz crystal microbalance (QCM, also known as bulk acoustic wave sensors);103−106 surface acoustic wave (SAW) sensors107−109 are a related class of sensors based on two or more interdigitated transducers placed on the surface of a piezoelectric substrate that measure delay in surface waves from one transducer to a second through the piezoelectric. For a QCM, a quartz resonator is made by cutting along a particular crystal direction to endow the device with a thickness shear mode, which makes use of a shear wave that has extremely low velocity in the fluid.105,110,111 Due to their effectiveness in the liquid phase, quartz crystal microbalances have been used for aqueous biosensing104,112 and immunosensing.106,113 Arrays of QCM or SAW sensors have been used to detect and distinguish a wide range of chemical analytes, including industrial toxins, chemical hazards, and biomolecules such as organophosphates,114 aromatic and halogenated hydrocarbons,115−117 chemical warfare agents,118 small molecular biotoxins,113 and HCN.119 QCMs have also shown promising results in the in situ analysis of solution supersaturation during cooling crystallization,120 and the characterization of metallic or polymeric nanoparticle size achieves results comparable to those determined by transmission electron microscopy (TEM) or dynamic light scattering (DLS).121

1.1. Nonoptical Sensors

The mammalian olfactory system is, in a way, a large array of bioelectrical receptors. Similarly, electrochemical sensors are made of resistors or capacitors as electronic units that keep track of changes in conductivity or capacitance during interactions between analyte molecules and the electrically active surface.64−67 Other grouping criteria include the detection basis (i.e., material vs geometry change), the arrangement (i.e., single versus differential), the size of the sensor, the reachable resolution, and the type of readout circuit.68 Chemiresistive or chemicapacitive sensors are straightforward to fabricate: a pair of parallel electrodes placed on a substrate and separated by a dielectric material, where the sensing component is coated or drop-cast to tune the electrochemical reactivity. An interdigitated electrode array is often used to adjust overall resistance or capacitance. In attempts to mimic the olfactory receptors, a broad range of electrochemical sensors made of different materials have been explored and designed. The most widely used electrochemical sensors include metal oxide chemiresistive semiconductors (e.g., SnO2),69,70 organic field-effect transistors (OFETs),71−74 conductive polymers of both inherently conductive (e.g., polythiophenes)75 and those integrated with conductive particles (e.g., graphene− or carbon nanotube−polymer composite).76−79 There are several diverse types of electrochemical sensors that have been successfully used in a broad class of real-world applications; this, however, goes beyond the scope of this review. For more details of electrochemical sensors, the readers can refer to recent publications on environmental,80 biosensing and immunosensing,81−84 food and beverage,85−87 clinical,88,89 and security screening90,91 applications. The most common class of electrochemical sensors are metal oxide sensors (MOSs), a type of chemiresistors,1,3,92 which are usually heated and react with volatile organic analytes to produce changes in electrical properties (e.g., resistivity or capacitance). The primary drawback of the use of traditional electrochemical sensors (e.g., unmodified metal oxide sensors or conductive polymers) for chemical sensing lies in the nearly indistinguishable sensor responses among similar analytes. This is due to the nature of those specific types of sensors in that they rely fundamentally on physical adsorption or nonspecific chemical interactions between the chemical analytes and the sensor receptors. The reliance on physical adsorption, in most cases, leads to poor selectivity of electrochemical sensors toward targeted analytes as well as interference from ambient humidity, which greatly restricts particularly the field usage of this type of sensor. In addition, baseline drift of sensor response resulting

1.2. Optical Sensors

Optical chemical sensors use infrared, visible, or ultraviolet light to probe chemical interactions at liquid or solid interfaces.122 The classification of optical sensors is associated with the nature of the transduction mechanisms on which they are based, such as absorbance, scattering, diffraction, reflectance, refraction, and luminescence (including photo-, chemi-, electrochemi-, or bioluminescence). Different regions of the electromagnetic C


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emitting a photon from an excited singlet state (Figure 2a); phosphorescence results instead when the excited singlet state first undergoes a forbidden transition to an excited triplet state, which then subsequently relaxes to the ground state (Figure 2b).133,134 Fluorescence measurements take advantage of a variety of parameters (e.g., fluorescence intensity, anisotropy, lifetime, emission and excitation spectra, fluorescence decay, and quantum yield) for data analysis, thus conferring substantial flexibility to these approaches.135,136 Generally, fluorescence techniques can be divided into three major classes: intrinsic fluorescence,137−140 extrinsic fluorescence,141,142 and differential fluorescent probes.46,143,144 Colorimetry, i.e., quantitative measurement of UV−vis absorbance or reflectance, is one of the oldest analytical methods,145 dating back to even long before the beginning of chemistry with simple “naked-eye” observations: there are ancient Chinese medicine books, for example, that mention color changes of silver needles or spoons to detect poisons (e.g., arsenic sulfides) in food.146 Colorimetric sensing is a fairly straightforward technique, and the advent of universal digital color imaging32,50,58,147 has diversified portable and effective detection methods. While many colorimetric sensors make use of the traditional three-channel visible range (i.e., partially overlapping wavelength ranges corresponding to red, green, and blue, RGB), sensors can also use a larger number of channels with a narrower spectral range for each (i.e., hyperspectral imaging), incorporate nonvisible wavelengths from near IR to UV, or span this full wavelength range using hundreds of color channels (i.e., full spectrophotometry). To simplify data analysis and instrumentation, colorimetric methods often analyze spectra only at a few discrete wavelengths (e.g., by using RGB color imaging) or by selecting the highest peaks in UV−vis spectra. There are two fundamental requirements for the design of optical sensors: they must be able to interact at least somewhat selectively with analytes, and they must report or provide feedback on such interactions through chromophores or fluorophores, preferably with very high extinction coefficients or high quantum yields, respectively. Such optical sensors may be semiselective (i.e., cross-reactive with multiple analytes) or

spectrum are employed with the use of different optical transduction methods, and a diverse set of parameters can be measured for each; these include intensity, lifetime, polarization, quantum yield, and quenching efficiency.2,49 In general, colorimetric and fluorometric sensors consist of four key elements: a light source, a wavelength selection device (e.g., filters or monochromator), a substrate or sample cell where changes in absorbed or emitted light occur in the presence of analytes, and a detector which is sensitive at the wavelength of interest (Figure 1). Most recently, rapid growth of the number of

Figure 1. Scheme of a general spectroscopic setup: (a) reflection, (b) refraction, (c) absorption, and (d) fluorescence emission. Reproduced with permission from ref 62. Copyright 2013 Royal Society of Chemistry.

efficient and integrated optical sensors has greatly facilitated the development of new sensing platforms, including fiber optic sensors,123−125 planar waveguide devices,126 and sensors based on surface enhanced Raman spectroscopy (SERS).127−129 This section will focus on the basis and classifications of colorimetric and fluorometric sensor arrays as well as their optical transduction methods involving UV−vis absorbance, reflectance, fluorescence, and nanoparticle-based surface plasmon resonance, along with the introduction of several new types of imaging platforms. There are other classes of optical sensors, based on chemiluminescent or bioluminescent systems, and these are discussed elsewhere in the literature.130−132 Fluorescence is the most commonly used spectroscopic method due to its higher sensitivity compared to most other optical sensors. Fluorescence occurs when an electron from a molecule is excited and then relaxes to the ground state by

Figure 2. Electronic transition leading to (a) fluorescence emission at λF and (b) phosphorescence emission at λP. Adapted with permission from ref 1. Copyright 2009 Springer. D


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in a similar manner, can incorporate a wide range of crossreactive sensor elements for pattern-based interactions with any given set of analytes.

highly selective (i.e., specific for only a single analyte or class of analytes). Structurally, optical sensors must thus contain a probe moiety to provide some degree of molecular recognition through interactions with the analytes and a reporter moiety for optical transduction; a single molecule may (and often does) serve both purposes. Dyes (i.e., molecular chromophores) and nanoporous pigments (i.e., insoluble colorants) are often chemoresponsive; that is, their colors (or fluorescent properties) are dependent upon their chemical environment. pH indicators are an obvious early example.148−150 In general, pigments, even as micrometer sized solid particles, do not act well as sensors because the very large majority of chromophores are not accessible to analytes; a notable exception is the class of nanoporous pigments, where the colorant centers are exposed to analytes.151−154 While many chemical dyes and fluorophores satisfy the requirements of semiselective sensors, there are also a considerable number of sensors (especially supramolecular receptors) that interact very selectively with specific analytes but do not respond via changes in their optical spectra. Macrocyclic structures including cyclodextrins, calixarenes, cyclophanes, crown ethers, cryptands, and cucurbiturils are generally spectroscopically inactive but often display excellent molecular recognition of guest species (e.g., ions and neutral ligands).155−157 In order to convert these supramolecular receptors into sensors, suitable chromophores or fluorophores need to be attached to the macrocycle in a fashion that leads to changes in optical signals upon analyte binding. For example, a Li+-specific sensor based on a novel lithium fluoroionophore and its polymer derivative has been successfully applied to the clinical monitoring of cation concentrations in blood (Figure 3).158 The fluoroionophore is built on a

2.1. Basis of Intermolecular Interactions

In applying the concept of pattern recognition to sensor arrays, the selection of intermolecular interactions is critical to the construction of effective colorimetric or fluorometric arrays. Fundamentally, chemical sensing is molecular recognition, and molecular recognition is the consequence of interactions between molecules.160−162 As shown in Figure 4, there is a

Figure 4. Strength of physical or chemical intermolecular interactions on a semiquantitative scale of enthalpy change. Such interactions are on a continuum from the very weakest van der Waals to the very strongest covalent or ionic bonds. Reproduced with permission from ref 62. Copyright 2013 Royal Society of Chemistry.

wide range of different types of intermolecular interactions that generate a continuum in strength of interaction (i.e., change in enthalpy), from the weakest of interactions such as van der Waals force to the strongest of covalent or ionic bonds. There is a seamless transition from electrostatic ionic bonding, covalent or coordination bond formation, Brønsted or Lewis acid−base interactions, hydrogen or halogen bonding, charge-transfer and π−π stacking complexation, dipolar or multipolar interactions, and van der Waals and other nonspecific interactions (e.g., quadrupole−dipole). The advantage of incorporating stronger interactions for sensor arrays is to achieve both greater intrinsic sensitivity and greater chemical selectivity. Coordination of some Lewis base analytes (e.g., amines, thiols) gives a relatively high enthalpy change ranging from ∼40 to ∼300 kJ/mol. In contrast, the enthalpy change of physical absorption of analytes (e.g., into conductive polymers) or adsorption (e.g., onto the surface of metal oxide semiconductors) is only ∼5 to 10 kJ/mol. The equilibrium constant of a typical coordination effect to metal ions is ∼104 times higher than that of a typical physisorption process. More importantly, stronger interactions bring a much wider range of chemical interactions than simple physical absorption, and therefore one may probe a much higher dimensionality and greatly improve the capability of distinguishing highly similar compounds or complex mixtures. Remarkably, almost all prior electronic noses (i.e., metal oxide or conductive polymer sensors) relied exclusively on van der Waals or physical adsorption as the primary interaction of analytes with the sensor: these are the weakest and least specific of sensor−analyte interactions. Disposable colorimetric sensor arrays, however, provide a successful approach to overcome the limitations of nonspecific interactions and to negotiate the opposite trend in sensor sensitivity vs robustness, as discussed in section 1. Colorimetric sensor arrays revisit an earlier, pre-

Figure 3. Structure of fluoroionophore that shows selective binding to Li+. Reproduced from ref 158. Copyright 2007 American Chemical Society.

tetramethyl “blocking subunit” of a 14-crown-4 as a selective binding site of Li+, and 4-methylcoumarin is employed in this case as a fluorophore. The sensor permits ratiometric detection via the characteristic blue shift and quenching of the fluorescence emission toward Li+. The sensor also exhibits good reversibility and is free from the interference of pH change and the other major biological cations (e.g., K+, Ca2+, and Mg2+).

2. OPTICAL ARRAY SENSING: CONCEPTS AND SENSORS The mammalian olfactory system allows for the discrimination among a huge number of chemical compounds or composite mixtures over an enormous range of concentrations. Such high specificity and efficiency derive from the pattern recognition by the forebrain’s olfactory bulb of the responses from hundreds of different types of olfactory receptor epithelial cells.159 This type of molecular recognition is exactly an opposite case to the traditional prototype of biospecificity, i.e., the lock-and-key model of enzyme−substrate interaction. Optical array sensing, E


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Figure 5. Example of a 1 × 40 linearized colorimetric sensor array using a wide range of chemical dyes, and cartridge packing of the array for gas sensing. Reproduced with permission from ref 32. Copyright 2016 Royal Society of Chemistry.

electronic era of analytical chemistry in many aspects,148,163−165 but with the addition of modern digital imaging imaging platforms for accurate, prompt, and reproducible data quantification.50,58,166−168 Based on the chemical properties of sensor elements, an array can probe a range of analyte−sensor interactions to generate a wide span of molecular specificity.27,169 At one end, there are individual sensors that are fairly “promiscuous”, i.e., highly crossreactive but less specific; these include polymers and polymer blends with optical receptors that adsorb analytes primarily based on hydrophobicity.170,171 Promiscuous sensors can contribute to the overall response of the sensor array but are insufficient to provide deep differentiation among similar analytes. At the other end, there are highly selective, or “monogamous” sensors that respond exclusively to one analyte or perhaps one closely related class of analytes. While monogamous receptors can produce high specificity for specific analytes, alone they will not form a sensor array that enables the recognition of other groups of analytes and mixtures;172 in addition, the design and synthesis of such specific, “monogamous” sensors can be time-consuming and complicated. The optimum optical sensor array will therefore incorporate a range of colorimetric or fluorometric sensor elements with a diversity of specificities and a wide range of chemical interactions.

play a role in the improvement of their chemical selectivity, either by modifying the local environment of the dye or by immobilizing the dye molecules in a sterically confining surrounding (e.g., molecularly imprinted polymers). The early versions of colorimetric sensor arrays50,173 were made of porphyrins and metalloporphyrins as sensor components and utilized mainly Lewis interactions with the metal and Brønsted interactions with the free base porphyrins. With the addition of a wider range of chemical dyes, the diversity of sensors has been impressively broadened over the past decade.27,169 For example, a recently developed 40-element sensor array comprising a wide range of chemoresponsive dyes has shown promising applications in the detection of toxic or explosive vapors (Figure 5).27,32,174,175 The choice of individual sensor elements in an colorimetric or fluorometric sensor array is fundamentally determined by its intended use: for example, is the array meant for a broad range of analyte detection or will it be used for a specialized class of analytes only? If one uses probes that only measure local polarity (e.g., solvatochromic or vapochromic fluorescent probes doped into various polymers176), then one may lose the opportunity for effective detection of different, but somewhat similar polar compounds. Keep in mind that potential analytes vary in many aspects of their chemical properties: solubility, hydrophilicity, redox, hydrogen bonding, Lewis donor/acceptor, and proton acidity and basicity of targets need to be taken into account. In general, a comprehensive optical sensor array for general sensing purposes should integrate as much chemical diversity among the individual sensor components as possible. Given the presence of metal ion binding sites in the olfactory receptors themselves,10−12 inclusion of metal-ion-containing dyes plays an important role in the construction of a chemoresponsive sensor array. One must also consider the presence of possible interferents by ambient, complex environments that may cause false positive responses. Finally, the dye properties themselves must be considered: stability of the printed dyes, printability of the dye formulation, and quantitative contribution of the dye to both the responsiveness and the dimensionality of the array. While these criteria can be applied quantitatively in evaluating the importance of the addition of a new dye to the array, fundamentally the tests are empirical and screening of dyes and dye formulations is inescapable. 2.2.1. Lewis Acid/Base Dyes. 2.2.1.1. Lewis Acidic Dyes. Most of the strongly odiferous compounds are Lewis bases: amines, carboxylic acids, sulfides, and phosphines. Not

2.2. Classification of Colorimetric and Fluorometric Sensor Elements

As mentioned, two structural features are essential to the design of colorimetric or fluorometric sensors: functionality sites to interact with analytes, and a chromophore or fluorophore to couple with the active site. The first factor implies that it would be highly advantageous to have multiple classes of strong chemical interactions involved, other than simply van der Waals or physisorption. Based on the types of intermolecular interactions that can induce significant colorimetric or fluorometric changes, one may divide cross-reactive, chemoresponsive dyes into five classes (albeit with some overlap): (i) Brønsted acidic or basic dyes (e.g., various pH indicators), (ii) Lewis acid/base dyes (e.g., metal complexes with open coordination sites or metal-ioncontaining chromogens), (iii) redox dyes, (iv) colorants with large permanent dipoles (i.e., zwitterionic vapochromic or solvatochromic dyes) for detection of local polarity or hydrogen bonding, and (v) chromogenic aggregative materials (e.g., plasmonic nanoparticles and nanoscale transition metal sulfides). In addition, the matrix holding those dyes also can F


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Figure 6. Structures of representative chemoresponsive dyes, including porphyrins or porphyrinoids, and others containing Lewis acid metal ions.

colorimetric50,61,177,180,190 or fluorometric167,191 (for d10 transition metals primarily) detection of metal-ligating volatiles. Representative examples of porphyrins, porphyrinoids, and other types of Lewis acid/base dyes that have been used as optical sensors are shown in Figure 6. 2.2.1.2. Lewis Acidic Dyes for Anion Detection. The coordination of anions was a long-overlooked area of inorganic chemistry. The biological and medical significance of many anions, from the simple (Cl−, F−, NO3−, PO43−, H2PO42−, etc.) to the complex (e.g., ATP, lipid anions, nucleic acids, and other phosphorylated biomolecular ions), has demanded and received much greater attention in recent years.192 Anion recognition chemistry also plays an essential role in catalysis and environmental sciences. Recently, substantial efforts have been made in the design of anion receptors for sensing by colorimetric or fluorometric means. The use of Lewis acidic dyes for the detection of anions has been extensively reviewed recently.193−208 Unique challenges still remain in anion complexation. Anion receptors can be neutral or positively charged and anion−receptor interactions are often dominated by electrostatic forces or hydrogen bonding. To build an anion sensor, one can use a Lewis acid that is inherently fluorescent or combine a chromogenic or fluorescent reporter moiety with a specific chelating receptor. Dye displacement assays, indicators with urea, thiourea, or naphthalimide, and metal ion containing chromogens (especially lanthanide and labile d8 and d10 transition metal ions), have been extensively explored in the past few years for the colorimetric or fluorescent detection of anions.209−212 As an example, Kakuchi and co-workers have developed a novel poly(phenylenebutadiynylene) fluorescent probe that contains urea functionalities for anion detection (Figure 7).213 A fluorescence turn-on response is ascribed to an anion-triggered disassembly process of the initially formed polymeric aggregates. The sensor allows for accurate discrimination of eight different anions at ∼1 mM with distinct fluorescent intensities. Using aggregated polymers with rationally designed functionalities as

coincidentally, these are also among the most common volatile metabolites of microbes; arguably, the primary function of the olfactory system is to keep our body away from high concentrations of bacteria or other microorganisms, and hence the location of our nostrils immediately above the mouth! Inspired by the important role that metal-binding sites of olfactory receptors play in sensing such Lewis bases,10−12 Lewis acid dyes are an obvious sensor choice. Among Lewis acidic dyes, metalloporphyrins50,61,177−180 are a popular choice for the detection of metal-ligating volatiles due to the open axial coordination sites and the large color changes from both wavelength and intensity shifts of strong π−π* absorbances upon ligand binding. Metalloporphyrins can be readily modified to adjust their chemical reactivity by changing metal centers or peripheral substituents to provide shaped pockets that restrict the access to the metal binding sites. This steric effect was first explored by the Collman group181,182 using picket-fence Fe(II) porphyrins for reversible binding of O2, and later expanded by other groups. Of special interest was Suslick’s development of a series of shape-selective, bis-pocket metalloporphyrins183−189 that display distinctive steric hindrance toward bonding sites, thus demonstrating potential uses as colorimetric sensors in the discrimination of linear vs branched amines.173 A wide range of both ligating volatile organic compounds (VOCs) (e.g., amines, carboxylic acids, phosphines and phosphites, thiols) will generate large color changes with metalloporphyrin sensors.50,61,177−180 Indeed, examples of metalloporphyrins as strong Lewis acid indicators can be found in daily life. The difference in color of scarlet red arterial blood versus the purple of venous blood is a natural example of the colorimetric detection of O2 using porphyrins. In addition to the intrinsic binding, porphyrins also possess excellent solvatochromic properties that lead to distinguishable colorimetric changes before and after interactions even with analytes that lack strong ligating functionalities (e.g., arenes, halocarbons, or ketones).50 Therefore, metalloporphyrins and their derivatives are an ideal group of dyes for G


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chemistry finds its origins in the design of crown ethers, cryptands, cyclodextrins, and calixarenes, whose sizes govern their specific binding of metal ions.155−157 Indeed, the beginning of the use of semispecific chelating Lewis acidic dyes as colorimetric sensors for metal cation detection,158,214−217 or socalled complexometric indicators (Figure 8),218 dates back over 150 years. Many of the traditional complexometric indicators were discovered in the early 19th century from nature products and are widely manufactured and used as histological stains nowadays. Complexometric indicators219,220 have chelating sites that enable strong coordination with metal ions and induce a rapid color change, often with significant selectivity among possible metal ions. These ionochromic dyes, or pM indicators (as a class of analogues to pH indicators) are designed to bring about a color change during the interaction any given metal ion.216,221 Complexometric indicators, depending on their chemical structure, may have greater or lesser degrees of specificity: as examples, Eriochrome Black T is used to detect Ca2+, Mg2+, and Al3+; calcein is used for Ca2+; hematoxylin is used for Cu2+; murexide is used for Ca2+, Ni2+, and rare earth ions; and xylenol orange is used for Ga3+, In3+, and Sc3+. The classical complexometric titrations are on the basis of displacement reactions, which start with the metal ions bound to the indicator and then replaced by the addition of EDTA, so the free dye molecule (rather than the metal ion complex) acts as the end point indicator. The limited selectivity of indicators and the presence of multiple pKa values of the chelators, however, usually require the addition of masking agents and a careful control of pH during the titration. Those strict requirements call

Figure 7. Schematic illustration of fluorescence turn-on sensing of anions based on disassembly of initially nonfluorescent (self-quenched) polymer aggregates upon anion binding. Reproduced from ref 213. Copyright 2012 American Chemical Society.

novel sensor elements has proven to be a promising strategy for anion sensing and contributes greatly to the understanding of supramolecular chemistry of anions. 2.2.1.3. Lewis Basic Dyes for Cation Detection. Lewis bases include mostly chelating and macrocyclic ligands that can have extremely high affinities for Lewis acids. Modern supramolecular

Figure 8. Complexometric indicators. (a) Several traditional indicators used for complexometric titrations. (b) Representative metal complexes of calcein, murexide, and EDTA, from top to bottom. H


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Figure 9. Schematic illustration of ion-selective nanospheres for complexometric titration of Ca2+. Solvatochromic dye resides in the nanospheres when no Ca2+ is present, while it is exchanged by Ca2+ into the aqueous solution at the end point, with a color transition from blue to pink. Reproduced from ref 224. Copyright 2015 American Chemical Society.

Figure 10. Some naturally occurring pH indicators. Litmus is from a lichen, delphinidin from cabernet sauvignon, cyanidin from blueberries, and rosinidin from rose periwinkle.

2.2.2. Brønsted Acid/Base Dyes. The origins of chemistry as a discipline are closely related to our obsession with “pretty colors”, and the contribution of the dye industry to the early development of chemistry cannot be understated.226−228 The colors of Brønsted acids or bases are pH-dependent; i.e., their UV−vis absorption spectra change through protonation or deprotonation as the pH changes. Litmus, or 7-hydroxyphenoxazone, is a representative pH indicator that was available to alchemists even in medieval times; litmus literally means “colored moss” in Old Norse, which is extracted from a mixture of lichens, particularly Roccella tinctoria in South America. There are dozens of pH indicators that can be obtained naturally from many plants, especially the anthocyanin dyes that are abundant in blueberry, raspberry, black rice, red cabbage, and black soybean (Figure 10). Synthetic pH indicators received tremendous attention during the first half of the 20th century,148 but even now there is substantial exploration of new pH indicator formulations.149 For example, there are recent developments of indicator nanoprobes using indicators immobilized in polymer hydrogels for intracellular sensing,229 and a wide range of organic

for a new design of complexometric indicators that are pH independent, sensitive, and selective. Recent advances in this area have taken advantage of either cross-reactivity of solutionbased arrays of complexometric indicators, or pH-independent titration in a heterogeneous phase rather than a homogeneous aqueous phase. Successful examples include the use of a microtiter plate,222 an immersed membrane,223 and, very recently, an emulsified nanosphere224,225 for selective recognition of individual metal ions in water. As a recent example using a nanosphere emulsion, Bakker and co-workers developed pH-independent “optode” nanospheres as indicators for complexometric titrations (Figure 9), which can accurately quantify Ca2+ concentration in mineral water without interference from other metal ions.224 The nanospheres contain an ionic solvatochromic dye, ion exchanger, and ionophore: only the solvatochromic dye will be expelled into the aqueous solution at the end point, resulting in a significant colorimetric change. The titration curves are independent of pH change and have sharper end points than with previously reported complexometric sensors or any similar indicators. I


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Figure 11. Several some typical pH indicator dyes.

Figure 12. Structures of some common pH-independent redox dyes. (a) Six representative redox dyes. (b) Detection mechanism of triacetone triperoxide (TATP) using N-isopropyl-N′-phenyl-p-phenylenediamine. (c) Colorimetric recognition of general aldehydes and ketones using 2,4dinitrophenylhydrazine, 4,4′-azodianiline, and pararosaniline. Reproduced from ref 242. Copyright 2010 American Chemical Society. Reproduced with permission from ref 243. Copyright 2017 Wiley.

diphenylamine, eriogreen, fenamic acid, methylene blue, Nile blue, and 2,2′-bipyridine.237−240 Due to the participation of protons in the electron transfer process in most media, redox indicators are sometimes classified into two groups by whether they are pH dependent or not. For example, to build an optical sensor for sensitive and accurate determination of glucose (i.e., in the concentration range 10−6− 10−2 mol/L, with high reproducibility), a thionine-based reversible redox sensor was immobilized on gel beads to monitor the level of byproducts (e.g., a coenzyme, NADH) involving enzymatic redox reactions of glucose.241 A linear calibration range of 5.7 × 10−4−2.0 × 10−3 mol L−1 was achieved for glucose, with a relative standard deviation of 99% according to HCA, PCA, and SVM analysis. LODs of several representative ketones or aldehydes were calculated to range from 40 to 800 ppb, which are all below 10% of their respective PELs (permissible exposure limits) and substantially better than AC


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other optical, acoustic, or electrochemical methods in which LODs are generally observed to be at parts per million levels. 5.1.2. Toxic Industrial Chemicals. Toxic industrial chemicals (TICs) are chemically reactive species whose toxicities derive from a wide variety of specific chemical reactions with multiple biochemical systems in cells and organisms. Some acute toxins target specific and critical metabolic enzymes (e.g., HCN inhibits cytochrome c oxidase while phosgene inhibits pulmonary function); some cause cell lysis in the lungs creating pulmonary edema (e.g., HCl, HF); other potent oxidants or reductants (e.g., O3, phosphine) target various relevant biosystems. There remains an urgent need for rapid, sensitive identification and quantification of TICs,358 yet we have no miniaturized, inexpensive, and effective technology for personal dosimetry of TICs in the chemical workplace or in cases of emergencies such as industrial fires or chemical spills. The chemical workplace has no equivalent to a radiation badge for personal monitoring of exposure to TICs and to provide warning at IDLH (immediately dangerous to life or health) or PEL (permissible exposure limit) concentrations. There are numerous conventional methods for the detection of gas phase hazardous chemicals, including gas chromatography/mass spectrometry (GC/MS), ion mobility spectrometry (IMS), electronic noses or tongues, and of course colorimetric detectors tailored to specific single analytes. Most such detection techniques, however, suffer from severe limitations: GC/MS is expensive and generally nonportable; IMS has limited chemical selectivity; electronic nose technologies have restricted selectivity and specificity (due to their heavy reliance on weak interactions). Moreover, interference from large environmental changes in humidity or temperature remains highly problematic. Colorimetric sensor arrays, however, are exceptionally well designed to incorporate a diverse set of chemically responsive indicators for the detection, identification, and quantification of TICs.27,174,175 Suslick and co-workers developed the use of nanoporous sol−gel or plasticized pigments27,153,174,175 as the chemoresponsive elements in a series of extremely sensitive colorimetric sensor arrays. They selected high hazard TICs from the reports of the NATO International Task Force 40359 and examined the ability of their array to discriminate among 20 TICs (Figure 40); LODs for TICs are generally well below the PEL (in most cases below 5% of PEL) and all are below 100 ppb with the exception of formaldehyde, which has been subsequently resolved using a specific aldehyde-sensitive array that can detect as low as 40 ppb formaldehyde (Figure 39). The sensor array was able to accurately discriminate among those 20 TICs at both their IDLH concentrations within 2 min of exposure and PEL concentrations within 5 min of exposure; HCA showed no errors in misclustering and jackknifed LDA gave an error rate below 0.7% out of 147 trials (Figure 41). The colorimetric sensor array was not sensitive to changes in humidity or temperature over a substantial range. The sensor array has shown excellent stability and reproducibility that the response is independent of the fluctuation in relative humidity and the presence of various common gaseous or liquid interferents. While LODs are defined absolutely with respect to S/N, that term only defines at which concentration one can determine that a certain analyte is present. Limits of recognition (LORs) are much more useful to define the sensor’s discriminatory capability, but they are also library dependent (i.e., relying on the choice of analyte types). Figure 42 demonstrates the limit of recognition for a subset of five TICs (i.e., HCN, NH3, PH3, SO2,

Figure 41. HCA dendrogram for 20 TICs at IDLH concentrations and a control. All experiments were performed in septuplicate; no confusions or errors in clustering were observed in 147 trials. Reproduced from ref 175. Copyright 2010 American Chemical Society.

and NO2) is well below 5% of their PEL, which may become of special interest for epidemiological studies. Consistent with the array’s capability of discriminating among many possible TICs over a series of parts per million or sub parts per million concentrations below their PELs, PCA and LDA confirmed the high dimensionality of the data achieved by the colorimetric sensor array that requires 17 PCA dimensions to capture 95% of the total variance.175 Other studies of interest in the design of more specialized optical arrays for specific detection of TICs have been actively reported. For example, Hoang et al.360 developed a dyeimpregnated nanofiber sensor array for accurate quantification of gaseous ammonia between 0 and 100 ppm. The sensor’s detection sensitivity could be easily regulated using different amounts of acidic additives or types of pH indicators. Bang et al.154 synthesized organosilica microspheres incorporating pH indicators as nanoporous pigments used in an array to differentiate different aliphatic amines; the array also successfully discriminated a series of vapor concentrations of ammonia, with a reported LOD of 100 ppb (85% sensitivity and >79% specificity of all samples. The urine assay using a colorimetric

respiratory infections, albeit with inadequate success. The prototype colorimetric sensor arrays developed by the Suslick group for fungal467 and bacterial457 identification have shown some preliminary clinical success for breath diagnosis. Lim et al.474,475 designed a tuberculosis testing tool that incorporated a 73-indicator colorimetric sensor array for fingerprinting VOC AV


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classification accordingly increased from 63% of using only three channels of the composite without the supramolecular assembly to 95% when taking all six channels into account (Figure 74). More significantly, this method required the minimal sample quantity of ∼200 ng (∼1000 cells) for analysis and could become an ideal tool for microbiopsy-based cancer diagnosis.

sensor array offers a powerful tool for a quick and simple diagnosis of tuberculosis in low resource settings. Lung cancer detection via breath analysis using colorimetric sensing techniques has also been elucidated by Mazzone et al.476,477 at the Cleveland Clinic with promising classification results. The test revealed that, based on exhaled breath screening of 229 study subjects (92 with lung cancer and 137 as controls), lung cancer patients can be distinguished from control subjects with high accuracy (C-statistic 0.889 for adenocarcinoma vs squamous cell carcinoma), and the accuracy for identification of lung cancer can be further improved by adjusting clinical and breath predictors.477 The direct analysis of nonvolatile cancer cells or disease biomarkers in aqueous biological samples is also highly desirable. In an entirely different approach to cell differentiation, it is not surprising that different cell lines interact differently with different nanoparticles478,479 and that those interactions are strongly affected by the chemical nature of the nanoparticle surfaces, particularly as biomolecules adsorb onto nanoparticle surfaces forming a “protein corona”.480−483 Taking advantage of interactions between polymers/AuNPs and various biomolecules, the parallel soluble fluorescent displacement assays developed by Rotello and co-workers421,484−486 for protein detection have also been extended to identification of cancer cells. Very recently, they reported a nanosensor using cell lysates to rapidly profile the tumorigenicity of cancer cells.487 In addition to the aforementioned approach involving differential probes, this sensing platform used a host−guest interaction between the macrocyclic cucurbit[7]uril (CB[7]) and the ammonium head of gold nanoparticles to build the second recognition receptor that extends the number of dimensions within each sensor element from three to six (Figure 73). The overall accuracy in

6. CONCLUSIONS AND FUTURE CHALLENGES During the last decade, chemical sensing has witnessed rapid development in both sensing materials and analytical techniques. Array-based optical sensing has demonstrated its usefulness in addressing a wide range of analytical challenges. By using chemically diverse chemoresponsive dyes or biological receptors in combination with chemometric analysis, arrays can be designed to discriminate various structurally similar analytes and analyte mixtures. While many biological systems employ a lock-and-key method for molecular recognition (e.g., enzymes and antibodies), which requires a highly specific receptor for each substrate, this approach is not used by the olfactory system and does not work for artificial olfaction. Using customized receptors (biological or synthetic) is simply impractical for the overwhelming number of volatiles and volatile mixtures that one would like to detect. Instead, sensor arrays provide an alternative means of creating specificity through pattern recognition of the response of an array of highly cross-reactive sensors. With recent advances in optical array sensing, sensitive and reliable fingerprinting of both single compounds and complex mixtures has become possible over a wide range of analyte types. Sensor arrays comprising a number of different sensor elements have been employed for detection of both gaseous and aqueous samples. The primary feature of an advanced sensor array, as an analogue to the mammalian nose, is that it gives a composite response to mixtures, but one that provides discrimination even between highly similar complex mixtures. Another essential feature of colorimetric or fluorometric sensor arrays is that they probe chemical properties of analytes, rather than physical properties, giving highly discriminatory, specific responses to an enormous range of analytes. The result is high-dimensional data that cannot be reduced to just two or three dominant coordinates. The advances in chemometric analysis of high-dimensional data provide new methods for the optimal use of high-dimensional sensor arrays. These developments parallel the advances in pattern recognition demanded by the burgeoning fields of artificial intelligence and machine learning. Probing chemical properties for chemical sensing is a “good news/bad news” story. The good news is that most analytes of concern (e.g., toxic industrial chemicals) are, essentially by definition, highly reactive and therefore readily detected, even at sub parts per million concentration; this resolves some issues in false positives associated with traditional electronic nose and solid state chemical sensors. The bad news, nevertheless, is that some targeted analytes are less reactive and could not reach ideal sensitivity using chemical methods. One solution is to pretreat the analyte stream to produce, for example, partial oxidation products that are more reactive and more easily detectable by cross-reactive sensors. More selective methods of “activating” these analytes, especially in the presence of a considerable concentration of interferents, would greatly improve the sensing capability of current sensor arrays. The primary limitation of array-based sensing, however, is that it does not offer a component-by-component analysis for

Figure 73. Construction of a six-channel sensor in a single well. Quenched AuNP−fluorescent protein (BenzNP−FP) conjugates serve as differential probes for the detection of cell lysates, based on fluorescence signal changes in three emission channels. CB[7] is then added to the same well to gain three additional fluorescent channels based on the interactions between the analytes and newly formed composites incorporating CB[7]. Reproduced from ref 487. Copyright 2017 American Chemical Society. AW


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Figure 74. LDA classification of five human cancerous cell lines based on (a) only three channels of BenzNP−FPs, (b) only three channels of BenzNP−CB[7], and (c) the combinatory classification with all six channels. (d) Overall classification accuracy of three sensing systems. Reproduced from ref 487. Copyright 2017 American Chemical Society.

AUTHOR INFORMATION

composite mixtures. Most chemists naturally assume that the goal with any complex mixture is to obtain a complete quantitative analysis of each component, which, in some cases, is difficult to be accomplished using either a colorimetric or fluorometric sensor array. In practice, however, one seldom really wants to know, for example, what the thousand different components are in a cup of coffee.488 What one often wants to know is whether the coffee is roasted properly or burnt, its place of origin, and other issues of quality control and quality assurance: array-based sensing proves to be an excellent technique for those goals. The other great challenge of optical array sensing lies in its performance in practical applications. Despite the success of colorimetric or fluorometric array sensing achieved in controlled laboratory environments, there are still challenges to overcome before these methods become common in field use. In order to create array-based assays that can accurately predict the identity of unknown analytes, the response of unknown analytes to the array should be reproducible; the system has to be able to match responses from unknowns to responses from a training set of analytes; disturbances from possible interferents should be effectively eliminated. The development of portable, low-noise, and accurate optical instrumentation with the capability of onboard and real-time analysis has shown substantial progress over the past few years and begins to match the increasing pressure for real-world use.

Corresponding Author

*E-mail: [email protected]. ORCID

Zheng Li: 0000-0001-9066-5791 Kenneth S. Suslick: 0000-0001-5422-0701 Notes

The authors declare no competing financial interest. Biographies Zheng Li was born and grew up in Wuhu, Auhui Province, China. He received his B.S. in chemistry from Nanjing University in 2012, and his Ph.D. in chemistry from the University of Illinois at Urbana− Champaign in 2017 under the guidance of Prof. Kenneth S. Suslick. His research interests include the development of new chromogenic or fluorometric materials and the design of portable sensing devices for a wide range of applications in health diagnosis, security screening, and environmental monitoring as well as agricultural and food inspection. He is currently a postdoctoral scholar from Prof. Qingshan Wei’s group at the North Carolina State University. Jon R. Askim received his Ph.D. in chemistry from the University of Illinois in 2015 under the supervision of Prof. Kenneth S. Suslick, where he worked to develop novel optical sensor arrays as well as instrumentation and techniques for their application. He is currently a postdoctoral fellow at the National Institute of Standards and Technology in Gaithersburg, MD, where he is working on developing new sensor fusion techniques for imaging-based methods. AX


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(20) Montuschi, P.; Mores, N.; Trove, A.; Mondino, C.; Barnes, P. J. The Electronic Nose in Respiratory Medicine. Respiration 2013, 85, 72−84. (21) Di Natale, C.; Paolesse, R.; Martinelli, E.; Capuano, R. SolidState Gas Sensors for Breath Analysis: A Review. Anal. Chim. Acta 2014, 824, 1−17. (22) Capelli, L.; Sironi, S.; Del Rosso, R. Electronic Noses for Environmental Monitoring Applications. Sensors 2014, 14, 19979− 20007. (23) Albert, K. J.; Lewis, N. S.; Schauer, C. L.; Sotzing, G. A.; Stitzel, S. E.; Vaid, T. P.; Walt, D. R. Cross-Reactive Chemical Sensor Arrays. Chem. Rev. 2000, 100, 2595−2626. (24) Persaud, K.; Dodd, G. Analysis of Discrimination Mechanisms in the Mammalian Olfactory System Using a Model Nose. Nature 1982, 299, 352−355. (25) Mirica, K. A.; Azzarelli, J. M.; Weis, J. G.; Schnorr, J. M.; Swager, T. M. Rapid Prototyping of Carbon-Based Chemiresistive Gas Sensors on Paper. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, E3265−E3270. (26) Jayawardane, B. M.; McKelvie, I. D.; Kolev, S. D. Development of a Gas-Diffusion Microfluidic Paper-Based Analytical Device (Mpad) for the Determination of Ammonia in Wastewater Samples. Anal. Chem. 2015, 87, 4621−4626. (27) Lim, S. H.; Feng, L.; Kemling, J. W.; Musto, C. J.; Suslick, K. S. An Optoelectronic Nose for the Detection of Toxic Gases. Nat. Chem. 2009, 1, 562−567. (28) Prasad, R. M.; Lauterbach, S.; Kleebe, H.-J.; MerdrignacConanec, O.; Barsan, N.; Weimar, U.; Gurlo, A. Response of Gallium Nitride Chemiresistors to Carbon Monoxide Is Due to Oxygen Contamination. ACS Sens. 2017, 2, 713−717. (29) Su, S.; Wu, W.; Gao, J.; Lu, J.; Fan, C. Nanomaterials-Based Sensors for Applications in Environmental Monitoring. J. Mater. Chem. 2012, 22, 18101−18110. (30) Bright, C. J.; Nallon, E. C.; Polcha, M. P.; Schnee, V. P. Quantum Dot and Polymer Composite Cross-Reactive Array for Chemical Vapor Detection. Anal. Chem. 2015, 87, 12270−12275. (31) Li, Z.; Bassett, W. P.; Askim, J. R.; Suslick, K. S. Differentiation among Peroxide Explosives with an Optoelectronic Nose. Chem. Commun. 2015, 51, 15312−15315. (32) Askim, J. R.; Li, Z.; LaGasse, M. K.; Rankin, J. M.; Suslick, K. S. An Optoelectronic Nose for Identification of Explosives. Chem. Sci. 2016, 7, 199−206. (33) Hu, Z.; Deibert, B. J.; Li, J. Luminescent Metal-Organic Frameworks for Chemical Sensing and Explosive Detection. Chem. Soc. Rev. 2014, 43, 5815−5840. (34) Le, N. D. B.; Yazdani, M.; Rotello, V. M. Array-Based Sensing Using Nanoparticles: An Alternative Approach for Cancer Diagnostics. Nanomedicine (London, U. K.) 2014, 9, 1487−1498. (35) Tisch, U.; Haick, H. Chemical Sensors for Breath Gas Analysis: The Latest Developments at the Breath Analysis Summit 2013. J. Breath Res. 2014, 8, 027103. (36) Konvalina, G.; Haick, H. Sensors for Breath Testing: From Nanomaterials to Comprehensive Disease Detection. Acc. Chem. Res. 2014, 47, 66−76. (37) Tomita, S.; Niwa, O.; Kurita, R. Artificial Modification of an Enzyme for Construction of Cross-Reactive Polyion Complexes to Fingerprint Signatures of Proteins and Mammalian Cells. Anal. Chem. 2016, 88, 9079−9086. (38) De Luna, P.; Mahshid, S. S.; Das, J.; Luan, B.; Sargent, E. H.; Kelley, S. O.; Zhou, R. High-Curvature Nanostructuring Enhances Probe Display for Biomolecular Detection. Nano Lett. 2017, 17, 1289− 1295. (39) Huang, W.; Diallo, A. K.; Dailey, J. L.; Besar, K.; Katz, H. E. Electrochemical Processes and Mechanistic Aspects of Field-Effect Sensors for Biomolecules. J. Mater. Chem. C 2015, 3, 6445−6470. (40) Zhang, C.; Bailey, D. P.; Suslick, K. S. Colorimetric Sensor Arrays for the Analysis of Beers: A Feasibility Study. J. Agric. Food Chem. 2006, 54, 4925−4931. (41) Maynor, M. S.; Nelson, T. L.; O’Sulliva, C.; Lavigne, J. J. A Food Freshness Sensor Using the Multistate Response from Analyte-Induced

Kenneth S. Suslick is the Marvin T. Schmidt Research Professor of Chemistry at the University of Illinois at Urbana−Champaign and the George Eastman Professor at the University of Oxford for 2018−2019. Prof. Suslick received his B.S. from Caltech in 1974 and his Ph.D. from Stanford in 1978, and came to the University of Illinois immediately thereafter. Among his awards are the Centenary Prize and the Sir George Stokes Medal of the RSC, the MRS Medal, the ACS Nobel Laureate Signature and Cope Scholar Awards, the Helmholtz−Rayleigh Silver Medal of the Acoustical Society of America, and the Chemical Pioneer Award of the American Institute of Chemists. He is a Fellow of the National Academy of Inventors.

ACKNOWLEDGMENTS Z.L. acknowledges the postdoctoral fellowship from the Procter & Gamble Foundation. K.S.S. acknowledges past funding in this research area by NIH, DHS, NSF, and DoD. REFERENCES (1) Janata, J. Principles of Chemical Sensors, 2nd ed.; Springer: New York, 2009. (2) Gründler, P. Chemical Sensors, an Introduction for Scientists and Engineers; Springer-Verlag: Berlin, 2007. (3) Banica, F.-G. Chemical Sensors and Biosensors: Fundamentals and Applications; John Wiley and Sons: Chichester, U.K., 2012. (4) Buck, L.; Axel, R. A Novel Multigene Family May Encode Odorant Receptors: A Molecular Basis for Odor Recognition. Cell 1991, 65, 175−187. (5) Bushdid, C.; Magnasco, M. O.; Vosshall, L. B.; Keller, A. Humans Can Discriminate More Than 1 Trillion Olfactory Stimuli. Science 2014, 343, 1370−1372. (6) Mombaerts, P. Seven-Transmembrane Proteins as Odorant and Chemosensory Receptors. Science 1999, 286, 707−711. (7) Hawkes, C. H.; Doty, R. L. The Neurology of Olfaction; Cambridge University Press: 2009. (8) Buck, L. B. Unraveling the Sense of Smell (Nobel Lecture). Angew. Chem., Int. Ed. 2005, 44, 6128−6140. (9) McGann, J. P. Poor Human Olfaction Is a 19th-Century Myth. Science 2017, 356, eaam7263. (10) Wang, J.; Luthey-Schulten, Z. A.; Suslick, K. S. Is the Olfactory Receptor a Metalloprotein? Proc. Natl. Acad. Sci. U. S. A. 2003, 100, 3035−3039. (11) Block, E.; Batista, V. S.; Matsunami, H.; Zhuang, H.; Ahmed, L. The Role of Metals in Mammalian Olfaction of Low Molecular Weight Organosulfur Compounds. Nat. Prod. Rep. 2017, 34, 529−557. (12) Duan, X.; Block, E.; Li, Z.; Connelly, T.; Zhang, J.; Huang, Z.; Su, X.; Pan, Y.; Wu, L.; Chi, Q.; et al. Crucial Role of Copper in Detection of Metal-Coordinating Odorants. Proc. Natl. Acad. Sci. U. S. A. 2012, 109, 3492−3497. (13) Zarzo, M. The Sense of Smell: Molecular Basis of Odorant Recognition. Biological Reviews 2007, 82, 455−479. (14) Rock, F.; Barsan, N.; Weimar, U. Electronic Nose: Current Status and Future Trends. Chem. Rev. 2008, 108, 705−725. (15) Jurs, P. C.; Bakken, G. A.; McClelland, H. E. Computational Methods for the Analysis of Chemical Sensor Array Data from Volatile Analytes. Chem. Rev. 2000, 100, 2649−2678. (16) Wilson, A. D.; Baietto, M. Applications and Advances in Electronic-Nose Technologies. Sensors 2009, 9, 5099−5148. (17) Loutfi, A.; Coradeschi, S.; Mani, G. K.; Shankar, P.; Rayappan, J. B. B. Electronic Noses for Food Quality: A Review. J. Food Eng. 2015, 144, 103−111. (18) Broza, Y. Y.; Haick, H. Nanomaterial-Based Sensors for Detection of Disease by Volatile Organic Compounds. Nanomedicine 2013, 8, 785−806. (19) Zhang, C. C.; Chen, P. L.; Hu, W. P. Organic Field-Effect Transistor-Based Gas Sensors. Chem. Soc. Rev. 2015, 44, 2087−2107. AY


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The Optoelectronic Nose: Colorimetric and Fluorometric Sensor Arrays

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